CN106964314A - A kind of preparation method of efficient removal organic dyestuff and reusable edible adsorbent by raw material of industrial waste - Google Patents
A kind of preparation method of efficient removal organic dyestuff and reusable edible adsorbent by raw material of industrial waste Download PDFInfo
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- CN106964314A CN106964314A CN201710266966.3A CN201710266966A CN106964314A CN 106964314 A CN106964314 A CN 106964314A CN 201710266966 A CN201710266966 A CN 201710266966A CN 106964314 A CN106964314 A CN 106964314A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
- B01J2220/4825—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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Abstract
A kind of preparation method of efficient removal organic dyestuff and reusable edible adsorbent by raw material of industrial waste, industrial residue of the present invention efficiently utilizes the preparation method for being converted into sorbing material.The invention solves the problems that the waste material after biomass industrialized production primary production is wasted, traditional sorbing material specific surface area is small, adsorption capacity is low, the problem of recycling ability.Method：First, in waste material thermal conducting agent removal process；2nd, the adsorbent of high-specific surface area is prepared, efficient removal organic dyestuff and reusable edible adsorbent by raw material of industrial waste is obtained.The present invention is used for a kind of preparation method of efficient removal organic dyestuff and reusable edible adsorbent by raw material of industrial waste.
Description
Technical field
The preparation method for being converted into sorbing material is efficiently utilized the present invention relates to industrial residue.
Background technology
In recent years, cause environment dirty with the increasingly depleted of the fossil energies such as coal petroleum gas and using fossil energy
The problems such as dye, is increasingly serious, finds reproducible clean energy resource extremely urgent.Substituted because reproducible biomass energy has
Fossil energy and potentiality of the world today to energy demand are met, it is widely studied to obtain researcher in recent years, and its biomass is given up
Gurry (such as maize straw, corncob etc.) is converted into primary production (such as liquid fuel：Ethanol, fuel gas：Synthesis gas, and
Solid product：Functional sugar xylose), yet with the building-up process high expensive of primary production, cause primary production still can not be wide
General industrialized production, certainly, the waste material after primary production are inexpensively handled, and this is also to cause primary production to synthesize high expensive
One of the main reasons.Because porous carbon materials have good chemical inertness, there is preferable stability in acid or alkali systems,
Have the advantages that abundant functional group is contained on larger specific surface area and surface.It further investigation reveals that, nowadays in the treatment of waste water,
Porous carbon is with a wide range of applications as the sorbing material of organic dyestuff.But traditional sorbing material such as silica gel, activity
The specific surface area such as aluminum oxide and synthetic resin is small, limited sorption capacity, the problems such as reusable edible ability, it is difficult to meet big
The demand of the treatment of Organic Wastewater of scale.If this waste can be synthesized with larger specific surface area, abundant duct
Structure and surface have the carbon material of abundant functional group, and can be as the sorbing material for having super excellent adsorption capacity, that
, this can not only promote the production of primary production, the shortcomings of can also solving traditional sorbing material, while in a way
Alleviating energy crisis problem, is a kind of green, the strategy of sustainable development.
The content of the invention
The invention solves the problems that the waste material after biomass industrialized production primary production is wasted, traditional sorbing material specific surface area
Small, adsorption capacity is low, the problem of recycling ability, and providing a kind of efficient removal by raw material of industrial waste has engine dyeing
The preparation method of material and reusable edible adsorbent.
A kind of preparation method of efficient removal organic dyestuff and reusable edible adsorbent by raw material of industrial waste, tool
Body is followed the steps below：
First, in waste material thermal conducting agent removal process：
Waste residue after corncob industrialized production xylose and xylitol is tentatively sieved by 40 eye mesh screens, bulky grain is removed
Thermal conducting agent, obtains the preliminary waste material for removing impurity, is 0.5mol/L~3mol/L's by the preliminary waste material for removing impurity and concentration
Sodium hydroxide solution is mixed, and 0.5h~3h is stirred at room temperature, pretreated mixed material is obtained, by pretreated mixture
Material is placed in the water-bath that temperature is 20 DEG C~90 DEG C, ultrasonic 0.5h~2h, is then stood and suction filtration, is obtained filtered material,
Filtered material is placed in the baking oven that temperature is 80 DEG C~110 DEG C, dried to constant mass, what is obtained is dried solid
Body, dried solid is placed in container and ground, and is obtained the powder that particle diameter is 0.147mm~1.0mm, is by particle diameter
0.147mm~1.0mm powder is placed in high temperature pyrolysis device, be passed through into high temperature pyrolysis device inert gas 20min~
50min, under inert gas shielding, 200 DEG C~600 DEG C are warming up to by 2 DEG C/min~10 DEG C/min of programming rate by temperature,
Under conditions of temperature is 200 DEG C~600 DEG C, be carbonized 1h~4h, naturally cools to room temperature after carbonization, the sample after being carbonized
Product, the sodium hydroxide solution for being first 0.5mol/L~2mol/L with concentration by the sample after carbonization is cleaned, and then uses deionized water
Cleaning, is finally placed in the baking oven that temperature is 80 DEG C~110 DEG C, dries to constant mass, the carbon dust after the impurity that is removed；
The waste material of described preliminary removing impurity and volume of the concentration for 0.5mol/L~3mol/L sodium hydroxide solution
Than for 1:(5~40)；
2nd, the adsorbent of high-specific surface area is prepared：
Carbon dust, potassium hydroxide and nitrogen source after impurity will be removed to mix, biased sample is obtained, biased sample is placed in container
Middle grinding, obtains the sample that particle diameter is 0.147mm~1.0mm, is then addition in 0.147mm~1.0mm sample to particle diameter
Mass percent is 10%~90% ethanol, is placed in the water-bath that temperature is 20 DEG C~90 DEG C, ultrasonic 0.5h~2h, will be super
Sample after sound is placed in the baking oven that temperature is 80 DEG C~110 DEG C and dries 8h~16h, dried powder is obtained, after drying
Powder be placed in high temperature pyrolysis device, inert gas 20min~50min is passed through into high temperature pyrolysis device, in inert gas
Under protection, temperature is warming up to 350 DEG C~1050 DEG C by 2 DEG C/min~10 DEG C/min of programming rate, temperature be 350 DEG C~
Under conditions of 1050 DEG C, high-temperature activation 1h~6h is subsequently cooled to room temperature, obtains the sample after high-temperature activation, by high-temperature activation
The hydrochloric acid that sample afterwards is first 0.5mol/L~2mol/L with concentration is cleaned, in then being cleaned with deionized water and being to cleaning solution
Property, finally it is placed in the baking oven that temperature is 80 DEG C~110 DEG C and dries to constant weight, obtains the efficient removal by raw material of industrial waste
Organic dyestuff and reusable edible adsorbent；
The mass ratio of carbon dust and potassium hydroxide after described removing impurity is 1:(1~8)；Described removes after impurity
Carbon dust and the mass ratio of nitrogen source are 1:(0.1~3)；The quality of described mixed sample and mass percent be 10%~
The volume ratio of 90% ethanol is 1g:(1~5) mL.
The beneficial effects of the invention are as follows：
First, the use of industrial residue is raw material, is a kind of reproducible biological material, it is cheap and easy to get with rich reserves,
It is environment-friendly, and the features such as its utilization can be promoted to the industrialized production of primary production of biomass.
2nd, adsorbent prepared by the present invention has higher specific surface area, and specific surface area is up to 2025.8m2/ g, exceedes
The most of commercial activated carbons of in the market.
3rd, the adsorbent and the business carbon dust of high-quality that prepared by the present invention are contrasted as adsorbent, to initial organic contamination
The initial concentration of thing --- methylene blue is configured to 500mg/L, and adsorbent prepared by the present invention has highest adsorption capacity, passes through
The optimization of over-richness and pH, adsorption capacity reaches 2249mg/g, and this is an adsorptive value being unsurpassed in excellence, and can be widely applied to contain
The processing procedure of a large amount of organic dyestuff.
4th, the adsorbent for preparing that the present invention is provided has efficient recycle value.Adsorb organic pollution methylene
After blue dyestuff, it is desorbed by 60% ethanol, after six uses of circulation, adsorption capacity still keeps initial 68.7%, and
It is with low cost and adsorbent is prepared simply.
The present invention is for a kind of efficient removal organic dyestuff and reusable edible adsorbent by raw material of industrial waste
Preparation method.
Brief description of the drawings
Fig. 1 is that the waste material of the preliminary removing impurity described in the step one of embodiment one amplifies 2000 times of electromicroscopic photographs；
Fig. 2 is efficient removal organic dyestuff by raw material of industrial waste prepared by embodiment one and reusable edible absorption
The photomacrograph of agent；
Fig. 3 is efficient removal organic dyestuff by raw material of industrial waste prepared by embodiment one and reusable edible absorption
1000 times of electromicroscopic photograph is amplified in agent；
Fig. 4 is efficient removal organic dyestuff by raw material of industrial waste prepared by embodiment one and reusable edible absorption
5000 times of electromicroscopic photograph is amplified in agent；
Fig. 5 is efficient removal organic dyestuff by raw material of industrial waste prepared by embodiment one and reusable edible absorption
10000 times of electromicroscopic photograph is amplified in agent；
Fig. 6 is the carbon dust graph of pore diameter distribution removed after impurity prepared by the step one of embodiment one；
Fig. 7 is efficient removal organic dyestuff by raw material of industrial waste prepared by embodiment one and reusable edible absorption
The graph of pore diameter distribution of agent；
Fig. 8 is the graph of pore diameter distribution that commercial activated carbons are sorbing material；
Fig. 9 is the suction to organic dyestuff methylene blue adsorption number process when initial dye methylene blue concentration is 500mg/L
The detection figure of attached ability, 1 is efficient removal organic dyestuff by raw material of industrial waste prepared by embodiment one and recyclable profit
It is that commercial activated carbons are adsorbent with adsorbent, 2；
Figure 10 is that efficient removal organic dyestuff by raw material of industrial waste and reusable edible prepared by embodiment one is inhaled
The detection figure of the attached dose of adsorption capacity under different initial dye methylene blue concentration, 1 is that initial dye methylene blue concentration is
450mg/L, 2 be that initial dye methylene blue concentration is 900mg/L；
Figure 11 is that efficient removal organic dyestuff by raw material of industrial waste and reusable edible prepared by embodiment one is inhaled
The attached dose of detection figure under alkaline environment to organic dyestuff methylene blue adsorption number ability；
Figure 12 is that efficient removal organic dyestuff by raw material of industrial waste and reusable edible prepared by embodiment one is inhaled
Attached dose of repetitive cycling uses the variation diagram of the adsorption capacity of six times；
Figure 13 is that efficient removal organic dyestuff by raw material of industrial waste and reusable edible prepared by embodiment one is inhaled
The attached dose of adsorption capacity test chart to different organic dyestuff.
Embodiment
Technical solution of the present invention is not limited to the embodiment of act set forth below, in addition to each embodiment it
Between any combination.
Embodiment one：A kind of efficient removal organic dyestuff by raw material of industrial waste described in present embodiment
And the preparation method of reusable edible adsorbent, specifically follow the steps below：
First, in waste material thermal conducting agent removal process：
Waste residue after corncob industrialized production xylose and xylitol is tentatively sieved by 40 eye mesh screens, bulky grain is removed
Thermal conducting agent, obtains the preliminary waste material for removing impurity, is 0.5mol/L~3mol/L's by the preliminary waste material for removing impurity and concentration
Sodium hydroxide solution is mixed, and 0.5h~3h is stirred at room temperature, pretreated mixed material is obtained, by pretreated mixture
Material is placed in the water-bath that temperature is 20 DEG C~90 DEG C, ultrasonic 0.5h~2h, is then stood and suction filtration, is obtained filtered material,
Filtered material is placed in the baking oven that temperature is 80 DEG C~110 DEG C, dried to constant mass, what is obtained is dried solid
Body, dried solid is placed in container and ground, and is obtained the powder that particle diameter is 0.147mm~1.0mm, is by particle diameter
0.147mm~1.0mm powder is placed in high temperature pyrolysis device, be passed through into high temperature pyrolysis device inert gas 20min~
50min, under inert gas shielding, 200 DEG C~600 DEG C are warming up to by 2 DEG C/min~10 DEG C/min of programming rate by temperature,
Under conditions of temperature is 200 DEG C~600 DEG C, be carbonized 1h~4h, naturally cools to room temperature after carbonization, the sample after being carbonized
Product, the sodium hydroxide solution for being first 0.5mol/L~2mol/L with concentration by the sample after carbonization is cleaned, and then uses deionized water
Cleaning, is finally placed in the baking oven that temperature is 80 DEG C~110 DEG C, dries to constant mass, the carbon dust after the impurity that is removed；
The waste material of described preliminary removing impurity and volume of the concentration for 0.5mol/L~3mol/L sodium hydroxide solution
Than for 1:(5~40)；
2nd, the adsorbent of high-specific surface area is prepared：
Carbon dust, potassium hydroxide and nitrogen source after impurity will be removed to mix, biased sample is obtained, biased sample is placed in container
Middle grinding, obtains the sample that particle diameter is 0.147mm~1.0mm, is then addition in 0.147mm~1.0mm sample to particle diameter
Mass percent is 10%~90% ethanol, is placed in the water-bath that temperature is 20 DEG C~90 DEG C, ultrasonic 0.5h~2h, will be super
Sample after sound is placed in the baking oven that temperature is 80 DEG C~110 DEG C and dries 8h~16h, dried powder is obtained, after drying
Powder be placed in high temperature pyrolysis device, inert gas 20min~50min is passed through into high temperature pyrolysis device, in inert gas
Under protection, temperature is warming up to 350 DEG C~1050 DEG C by 2 DEG C/min~10 DEG C/min of programming rate, temperature be 350 DEG C~
Under conditions of 1050 DEG C, high-temperature activation 1h~6h is subsequently cooled to room temperature, obtains the sample after high-temperature activation, by high-temperature activation
The hydrochloric acid that sample afterwards is first 0.5mol/L~2mol/L with concentration is cleaned, in then being cleaned with deionized water and being to cleaning solution
Property, finally it is placed in the baking oven that temperature is 80 DEG C~110 DEG C and dries to constant weight, obtains the efficient removal by raw material of industrial waste
Organic dyestuff and reusable edible adsorbent；
The mass ratio of carbon dust and potassium hydroxide after described removing impurity is 1:(1~8)；Described removes after impurity
Carbon dust and the mass ratio of nitrogen source are 1:(0.1~3)；The quality of described mixed sample and mass percent be 10%~
The volume ratio of 90% ethanol is 1g:(1~5) mL.
Remove bulky grain thermal conducting agent to remove the sandy soil of bulky grain described in step one.
In step one, first, the hydrogen-oxygen for being 0.5mol/L~3mol/L by the preliminary waste material immersion concentration for removing sandy soil
Change in sodium solution, static placement 24h, it is therefore an objective to react part thermal conducting agent and sodium hydroxide, suction filtration removes reactant；This reality
Apply that the presence in view of thermal conducting agent is highly stable and biomass waste material itself contains substantial amounts of ash content, therefore be 400 DEG C in temperature
Under, then carbonization treatment is carried out, then the product after pyroreaction is cleaned, the purpose of removal of impurities has been reached, has been conducive to next step
The activation of activating reagent.In step 2, in order to obtain larger specific surface area, be mainly in view of potassium hydroxide
Effect, mainly produces the potassium and carbon monoxide largely flowed, so that producing abundant duct in carbon matrix inside carbon matrix
Reaction mechanism under structure, its high temperature is as follows：
K2CO3→K2O+CO2 (1)
K2O+C→2K+CO (2)
C+CO2→2CO (3)
Present embodiment innovative point is that the waste material after biomass industrialized production primary production is efficiently utilized, will
Its two step is converted into the sorbing material of high-quality, so as to solve wastage of material and reduce the cost of primary production, promotes once
The industrialized production of product, while the traditional sorbing material specific surface area of solution is small, adsorption capacity is low, recycles ability etc. and asks
Topic.
The beneficial effect of present embodiment is：
First, the use of industrial residue is raw material, is a kind of reproducible biological material, it is cheap and easy to get with rich reserves,
It is environment-friendly, and the features such as its utilization can be promoted to the industrialized production of primary production of biomass.
2nd, adsorbent prepared by present embodiment has higher specific surface area, and specific surface area is up to 2025.8m2/ g, surpasses
The most of commercial activated carbons of in the market are crossed.
3rd, the adsorbent and the business carbon dust of high-quality that prepared by present embodiment are contrasted as adsorbent, to initial organic dirt
Dye thing --- the initial concentration of methylene blue is configured to 500mg/L, and adsorbent prepared by the present invention has highest adsorption capacity,
Optimization through over-richness and pH, adsorption capacity reaches 2249mg/g, and this is an adsorptive value being unsurpassed in excellence, and be can be widely applied to
Processing procedure containing a large amount of organic dyestuff.
4th, the adsorbent for preparing that present embodiment is provided has efficient recycle value.Adsorb organic pollution sub-
After methyl blue dye, it is desorbed by 60% ethanol, after six uses of circulation, adsorption capacity still keeps initial
68.7%, and adsorbent preparation is simple, it is with low cost.
Embodiment two：Present embodiment from unlike embodiment one：Inertia described in step one
Gas is nitrogen；Inert gas described in step 2 is nitrogen.It is other identical with embodiment one.
Embodiment three：Unlike one of present embodiment and embodiment one or two：Institute in step one
The high temperature pyrolysis device stated is tube furnace；High temperature pyrolysis device described in step 2 is tube furnace.Other and specific embodiment party
Formula one or two is identical.
Embodiment four：Unlike one of present embodiment and embodiment one to three：Institute in step one
The container stated is agate mortar or alundum (Al2O3) porcelain Noah's ark；Container described in step 2 is agate mortar or alundum (Al2O3)
Porcelain Noah's ark.It is other identical with embodiment one to three.
Embodiment five：Unlike one of present embodiment and embodiment one to four：Institute in step 2
The nitrogen source stated is melamine.It is other identical with embodiment one to four.
Embodiment six：Unlike one of present embodiment and embodiment one to five：Will in step one
The preliminary waste material for removing impurity is mixed with concentration for 2mol/L sodium hydroxide solution, and 0.5h~3h is stirred at room temperature, obtains pre-
Mixed material after processing.It is other identical with embodiment one to five.
Embodiment seven：Unlike one of present embodiment and embodiment one to six：Will in step one
Pretreated mixed material is placed in the water-bath that temperature is 55 DEG C, and then ultrasonic 1h stands 24h and suction filtration, obtain after suction filtration
Material, filtered material is placed in during temperature is 105 DEG C of baking oven, dried to constant mass, what is obtained is dried solid
Body.It is other identical with embodiment one to six.
Embodiment eight：Unlike one of present embodiment and embodiment one to seven：In step one to
Inert gas 20min~50min is passed through in high temperature pyrolysis device, will by 3 DEG C/min of programming rate under inert gas shielding
Temperature is warming up to 400 DEG C, under conditions of temperature is 400 DEG C, and be carbonized 2h, naturally cools to room temperature after carbonization, obtains after carbonization
Sample.It is other identical with embodiment one to seven.
Embodiment nine：Unlike one of present embodiment and embodiment one to eight：In step 2 so
The ethanol that mass percent is 60% is added in the sample that backward particle diameter is 0.147mm~1.0mm, it is 55 DEG C to be placed in temperature
In water-bath, the sample after ultrasound is placed in the baking oven that temperature is 105 DEG C and dries 12h, obtains dried powder by ultrasonic 1h.
It is other identical with embodiment one to eight.
Embodiment ten：Unlike one of present embodiment and embodiment one to nine：In step 2 to
Inert gas 30min is passed through in high temperature pyrolysis device, under inert gas shielding, by 3 DEG C/min of programming rate by temperature liter
Temperature is to 850 DEG C, under conditions of temperature is 850 DEG C, high-temperature activation 2h.It is other identical with embodiment one to nine.
Beneficial effects of the present invention are verified using following examples：
Embodiment one：
A kind of preparation method of efficient removal organic dyestuff and reusable edible adsorbent by raw material of industrial waste is
Carry out according to the following steps：
First, in waste material thermal conducting agent removal process：
Waste residue after corncob industrialized production xylose and xylitol is tentatively sieved by 40 eye mesh screens, bulky grain is removed
Thermal conducting agent, obtains the preliminary waste material for removing impurity, and the preliminary waste material for removing impurity is molten for 2mol/L sodium hydroxide with concentration
Liquid is mixed, and 1h is stirred at room temperature, pretreated mixed material is obtained, and pretreated mixed material is placed in into temperature for 55 DEG C
Water-bath in, then ultrasonic 1h stands 24h and suction filtration, obtains filtered material, filtered material is placed in into temperature is
In 105 DEG C of baking oven, dry to constant mass, obtained dried solid, dried solid be placed in container and ground,
The powder that particle diameter is 0.147mm~0.42mm is obtained, particle diameter is placed in high temperature pyrolysis device for 0.147mm~0.42mm powder
In, inert gas 30min is passed through into high temperature pyrolysis device, under inert gas shielding, by 3 DEG C/min of programming rate by temperature
Degree is warming up to 400 DEG C, under conditions of temperature is 400 DEG C, and be carbonized 2h, room temperature is naturally cooled to after carbonization, after being carbonized
Sample, the sodium hydroxide solution for being first 1mol/L with concentration by the sample after carbonization is cleaned, and is then cleaned with deionized water, finally
It is placed in the baking oven that temperature is 105 DEG C, dries to constant mass, the carbon dust after the impurity that is removed；
The volume ratio for the sodium hydroxide solution that the waste material of described preliminary removing impurity is 2mol/L with concentration is 1:20；
2nd, the adsorbent of high-specific surface area is prepared：
Carbon dust, potassium hydroxide and nitrogen source after impurity will be removed to mix, biased sample is obtained, biased sample is placed in container
Middle grinding, obtains the sample that particle diameter is 0.147mm~0.42mm, then adds into the sample that particle diameter is 0.147mm~0.42mm
Enter the ethanol that mass percent is 60%, be placed in the water-bath that temperature is 55 DEG C, the sample after ultrasound is placed in temperature by ultrasonic 1h
Spend and 12h is dried in the baking oven for 105 DEG C, obtain dried powder, dried powder is placed in high temperature pyrolysis device, to
Inert gas 30min is passed through in high temperature pyrolysis device, under inert gas shielding, by 3 DEG C/min of programming rate by temperature liter
Temperature is to 850 DEG C, and under conditions of temperature is 850 DEG C, high-temperature activation 2h is subsequently cooled to room temperature, obtains the sample after high-temperature activation
Product, the hydrochloric acid for being first 0.5mol/L with concentration by the sample after high-temperature activation is cleaned, and is then cleaned with deionized water to cleaning solution
For neutrality, finally it is placed in the baking oven that temperature is 105 DEG C and dries to constant weight, obtaining the efficient removal by raw material of industrial waste has
Engine dyeing material and reusable edible adsorbent；
The mass ratio of carbon dust and potassium hydroxide after described removing impurity is 1:3；The described carbon dust removed after impurity
Mass ratio with nitrogen source is 1:0.113；The quality of described mixed sample and body of the mass percent for 60% ethanol
Product is than being 1g:2mL.
Inert gas described in step one is nitrogen.High temperature pyrolysis device described in step one is tube furnace.Step
Container described in one is agate mortar.Nitrogen source described in step 2 is melamine.High temperature pyrolysis described in step 2
Device is tube furnace.Container described in step 2 is agate mortar.Inert gas described in step 2 is nitrogen.
Fig. 1 is that the waste material of the preliminary removing impurity described in the step one of embodiment one amplifies 2000 times of electromicroscopic photographs.By scheming
Understand, the scraped surface of preliminary removal of impurities is relative smooth, and completely.
Fig. 2 is efficient removal organic dyestuff by raw material of industrial waste prepared by embodiment one and reusable edible absorption
The photomacrograph of agent.
Fig. 3 is efficient removal organic dyestuff by raw material of industrial waste prepared by embodiment one and reusable edible absorption
1000 times of electromicroscopic photograph is amplified in agent；Compared with raw material, the particle diameter of adsorbent substantially diminishes, surface folding, and granular size is not
Uniformly.
Fig. 4 is efficient removal organic dyestuff by raw material of industrial waste prepared by embodiment one and reusable edible absorption
5000 times of electromicroscopic photograph is amplified in agent, is clear that stromal surface is all destroyed, it can be seen that uneven aperture.
Fig. 5 is efficient removal organic dyestuff by raw material of industrial waste prepared by embodiment one and reusable edible absorption
10000 times of electromicroscopic photograph is amplified in agent, and the section part being clear that in carbon matrix has formed abundant nano grade pore
Road, this is due to the effect of high-temperature activation reagent, and the duct of formation is conducive to the transmittance process of adsorbate.
Fig. 6 is the carbon dust graph of pore diameter distribution removed after impurity prepared by the step one of embodiment one；Fig. 7 is prepared by embodiment one
Efficient removal organic dyestuff by raw material of industrial waste and reusable edible adsorbent graph of pore diameter distribution；Fig. 8 is business
Activated carbon is the graph of pore diameter distribution of sorbing material；As seen from the figure, than there is substantial amounts of duct before activation after activation, its aperture point
Cloth is in 1.0~4.5nm, compared to commercial activated carbons (producer：Chinese Shanghai, which is closed, reaches carbon material Co., Ltd), it is prepared by embodiment one
Efficient removal organic dyestuff by raw material of industrial waste and reusable edible adsorbent possess substantial amounts of mesoporous 2.0~
4.5nm。
Fig. 9 is the suction to organic dyestuff methylene blue adsorption number process when initial dye methylene blue concentration is 500mg/L
The detection figure of attached ability, 1 is efficient removal organic dyestuff by raw material of industrial waste prepared by embodiment one and recyclable profit
It is that commercial activated carbons are adsorbent with adsorbent, 2；0.4g adsorbents are added in per 1L initial dye methylene blues, up to equilibrium state
When, efficient removal organic dyestuff by raw material of industrial waste and the energy of adsorption of reusable edible adsorbent prepared by embodiment one
Power is 1238.1mg/g, has surmounted commercial activated carbons (producer：Chinese Shanghai close reach carbon material Co., Ltd) absorption
Ability.
Figure 10 is that efficient removal organic dyestuff by raw material of industrial waste and reusable edible prepared by embodiment one is inhaled
The detection figure of the attached dose of adsorption capacity under different initial dye methylene blue concentration, 1 is that initial dye methylene blue concentration is
450mg/L, 2 be that initial dye methylene blue concentration is 900mg/L.0.4g absorption is added in per 1L initial dye methylene blues
Agent, when initial dye methylene blue concentration is 450mg/L, during up to equilibrium state, adsorption capacity is 1122.378mg/g, and removal efficiency is
99.77%；When initial dye methylene blue concentration is 900mg/L, during up to equilibrium state, adsorption capacity is 1570.204mg/g, is taken off
Except rate is 69.79%, with certain use value.
Figure 11 is that efficient removal organic dyestuff by raw material of industrial waste and reusable edible prepared by embodiment one is inhaled
The attached dose of detection figure under alkaline environment to organic dyestuff methylene blue adsorption number ability；Added in per 1L initial dye methylene blues
0.4g adsorbents, initial dye methylene blue concentration is 900mg/L, the pH to 11.65 of initial dye methylene blue is adjusted, in alkali
Property environment under, during absorption 120min, 2249mg/g is reached to the adsorption capacity of organic dyestuff methylene blue, removal efficiency is 99.96%.
Figure 12 is that efficient removal organic dyestuff by raw material of industrial waste and reusable edible prepared by embodiment one is inhaled
Attached dose of repetitive cycling uses the variation diagram of the adsorption capacity of six times；0.32g adsorbents are added in per 1L initial dye methylene blues
And initial dye methylene blue concentration be 450mg/L under conditions of, absorption completely after, by the adsorbent after absorption pass through quality hundred
Fraction is desorbed for 60% ethanol cleaning, and after recycled six times, its adsorption capacity remains in that initial 68.7%.
Figure 13 is that efficient removal organic dyestuff by raw material of industrial waste and reusable edible prepared by embodiment one is inhaled
The attached dose of adsorption capacity test chart to different organic dyestuff；0.133g adsorbents and not are added in per 1L initial dye methylene blues
With dyestuff initial concentration be 100mg/L when, detection absorption up to balance after, orange beta-naphthol Congo red to organic dyestuff, indigo two sulphur
The adsorption capacity of sour sodium and methyl orange is respectively 744.55mg/g, 724.03mg/g, 644.08mg/g, 463.01mg/g.
Complex chart 4, Fig. 5 and Fig. 7 understand that have successfully been obtained the function with abundant pore passage structure according to the present embodiment inhales
Enclosure material.Knowable to complex chart 9-13, the super large adsorption capacity that the present embodiment is successfully obtained and the suction with efficient reusable edible
In terms of attached dose can be used in organic toxicity dyestuff processing of industrial wastewater.
Claims (10)
1. a kind of preparation method of efficient removal organic dyestuff and reusable edible adsorbent by raw material of industrial waste, it is special
Levy be a kind of efficient removal organic dyestuff by raw material of industrial waste and reusable edible adsorbent preparation method be by
Carried out according to following steps：
First, in waste material thermal conducting agent removal process：
Waste residue after corncob industrialized production xylose and xylitol is tentatively sieved by 40 eye mesh screens, bulky grain heat conduction is removed
Agent, obtains the preliminary waste material for removing impurity, the hydrogen-oxygen for being 0.5mol/L~3mol/L by the preliminary waste material and concentration for removing impurity
Change sodium solution mixing, 0.5h~3h is stirred at room temperature, pretreated mixed material is obtained, pretreated mixed material is put
In temperature in 20 DEG C~90 DEG C of water-bath, then ultrasonic 0.5h~2h stands and suction filtration, obtain filtered material, will take out
Material after filter is placed in the baking oven that temperature is 80 DEG C~110 DEG C, is dried to constant mass, obtained dried solid, will
Dried solid be placed in container grind, obtain particle diameter be 0.147mm~1.0mm powder, by particle diameter be 0.147mm~
1.0mm powder is placed in high temperature pyrolysis device, inert gas 20min~50min is passed through into high temperature pyrolysis device, in inertia
Under gas shield, temperature is warming up to 200 DEG C~600 DEG C by 2 DEG C/min~10 DEG C/min of programming rate, is 200 in temperature
DEG C~600 DEG C under conditions of, be carbonized 1h~4h, naturally cool to room temperature after carbonization, the sample after being carbonized, after carbonization
The sodium hydroxide solution that sample is first 0.5mol/L~2mol/L with concentration is cleaned, and is then cleaned with deionized water, is finally placed in
Temperature is in 80 DEG C~110 DEG C of baking oven, drying is to constant mass, the carbon dust after the impurity that is removed；
The volume ratio for the sodium hydroxide solution that the waste material of described preliminary removing impurity is 0.5mol/L~3mol/L with concentration is
1:(5~40)；
2nd, the adsorbent of high-specific surface area is prepared：
Carbon dust, potassium hydroxide and nitrogen source after impurity will be removed to mix, biased sample is obtained, biased sample is placed in container and ground
Mill, obtains the sample that particle diameter is 0.147mm~1.0mm, then adds quality into the sample that particle diameter is 0.147mm~1.0mm
Percentage is 10%~90% ethanol, is placed in the water-bath that temperature is 20 DEG C~90 DEG C, ultrasonic 0.5h~2h, after ultrasound
Sample to be placed in temperature be to dry 8h~16h in 80 DEG C~110 DEG C of baking oven, dried powder is obtained, by dried powder
Body is placed in high temperature pyrolysis device, inert gas 20min~50min is passed through into high temperature pyrolysis device, in inert gas shielding
Under, temperature is warming up to 350 DEG C~1050 DEG C by 2 DEG C/min~10 DEG C/min of programming rate, is 350 DEG C~1050 in temperature
Under conditions of DEG C, high-temperature activation 1h~6h is subsequently cooled to room temperature, the sample after high-temperature activation is obtained, after high-temperature activation
The hydrochloric acid that sample is first 0.5mol/L~2mol/L with concentration is cleaned, and it is neutral then to be cleaned with deionized water to cleaning solution, most
It is placed in the baking oven that temperature is 80 DEG C~110 DEG C and is dried to constant weight afterwards, the efficiently removal obtained by raw material of industrial waste is organic
Dyestuff and reusable edible adsorbent；
The mass ratio of carbon dust and potassium hydroxide after described removing impurity is 1:(1~8)；The described carbon dust removed after impurity
Mass ratio with nitrogen source is 1:(0.1~3)；The quality of described mixed sample is 10%~90% with mass percent
The volume ratio of ethanol is 1g:(1~5) mL.
2. a kind of efficient removal organic dyestuff and reusable edible by raw material of industrial waste according to claim 1 is inhaled
Attached dose of preparation method, it is characterised in that the inert gas described in step one is nitrogen；Inert gas described in step 2
For nitrogen.
3. a kind of efficient removal organic dyestuff and reusable edible by raw material of industrial waste according to claim 1 is inhaled
Attached dose of preparation method, it is characterised in that the high temperature pyrolysis device described in step one is tube furnace；Height described in step 2
Warm pyrolysis installation is tube furnace.
4. a kind of efficient removal organic dyestuff and reusable edible by raw material of industrial waste according to claim 1 is inhaled
Attached dose of preparation method, it is characterised in that the container described in step one is agate mortar or alundum (Al2O3) porcelain Noah's ark；Step
Container described in two is agate mortar or alundum (Al2O3) porcelain Noah's ark.
5. a kind of efficient removal organic dyestuff and reusable edible by raw material of industrial waste according to claim 1 is inhaled
Attached dose of preparation method, it is characterised in that the nitrogen source described in step 2 is melamine.
6. a kind of efficient removal organic dyestuff and reusable edible by raw material of industrial waste according to claim 1 is inhaled
Attached dose of preparation method, it is characterised in that by the preliminary waste material for removing impurity and sodium hydroxide of the concentration for 2mol/L in step one
Solution is mixed, and 0.5h~3h is stirred at room temperature, pretreated mixed material is obtained.
7. a kind of efficient removal organic dyestuff and reusable edible by raw material of industrial waste according to claim 1 is inhaled
Attached dose of preparation method, it is characterised in that pretreated mixed material is placed in the water-bath that temperature is 55 DEG C in step one,
Ultrasonic 1h, then stands 24h and suction filtration, obtains filtered material, and filtered material is placed in into the baking oven that temperature is 105 DEG C
In, dry to constant mass, obtained dried solid.
8. a kind of efficient removal organic dyestuff and reusable edible by raw material of industrial waste according to claim 1 is inhaled
Attached dose of preparation method, it is characterised in that be passed through inert gas 20min~50min in step one into high temperature pyrolysis device,
Under inert gas shielding, temperature is warming up to 400 DEG C using programming rate as 3 DEG C/min, under conditions of temperature is 400 DEG C, carbon
Change 2h, naturally cool to room temperature after carbonization, the sample after being carbonized.
9. a kind of efficient removal organic dyestuff and reusable edible by raw material of industrial waste according to claim 1 is inhaled
Attached dose of preparation method, it is characterised in that add quality hundred in step 2 and then into the sample that particle diameter is 0.147mm~1.0mm
Fraction is 60% ethanol, is placed in the water-bath that temperature is 55 DEG C, ultrasonic 1h, and it is 105 that the sample after ultrasound is placed in into temperature
DEG C baking oven in dry 12h, obtain dried powder.
10. a kind of efficient removal organic dyestuff and reusable edible by raw material of industrial waste according to claim 1
The preparation method of adsorbent, it is characterised in that inert gas 30min is passed through in step 2 into high temperature pyrolysis device, in indifferent gas
Under body protection, temperature is warming up to 850 DEG C using programming rate as 3 DEG C/min, under conditions of temperature is 850 DEG C, high-temperature activation
2h。
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| CN115254003A (en) * | 2022-08-29 | 2022-11-01 | 哈尔滨工业大学（威海） | Porous layered K capable of efficiently adsorbing organic dye 2 Ti 8 O 17 Method for preparing nano crystal whisker |
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|---|---|---|---|---|
| CN105032362A (en) * | 2015-03-05 | 2015-11-11 | 中霖中科环境科技（安徽）股份有限公司 | Method of adsorbing printing and dyeing waste water with straw after plasma treatment |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105032362A (en) * | 2015-03-05 | 2015-11-11 | 中霖中科环境科技（安徽）股份有限公司 | Method of adsorbing printing and dyeing waste water with straw after plasma treatment |
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| JI ZHANG ET.AL: ""Study of chromium(VI) removal from aqueous solution using nitrogen-enriched activated carbon based bamboo processing residues"", 《THE ROYAL SOCIETY OF CHEMISTRY》 * |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115254003A (en) * | 2022-08-29 | 2022-11-01 | 哈尔滨工业大学（威海） | Porous layered K capable of efficiently adsorbing organic dye 2 Ti 8 O 17 Method for preparing nano crystal whisker |
| CN115254003B (en) * | 2022-08-29 | 2023-05-30 | 哈尔滨工业大学（威海） | Porous layered K capable of efficiently adsorbing organic dye 2 Ti 8 O 17 Process for preparing nano whisker |
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